Conversion process



E. B- FOUNTAIN CONVERSION PROCESS Filed Dec. 13, 1962 Dec. 15, v1964 250m2... m5525200 om w1 lV.. :mman N. om A .j w .J zomo ...TJ 1 i.- SE1 1 PENEOQ m .EMS \Nm \wm w. k I Y mw Nm ON Q i \O.v NN. r t w l wm\ ...L nl. r OIIYIV .vm om\ INVENTOR EUGENE B. FOUNTAIN BWMLQM Hi8 ATTORNEY United States Patent O 3,161,698 CONVERSION PROCESS Eugene B. Fountain, Berkeley, Calif., assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware Filed Dec. 13, 1962, Ser. No. 244,413 3 Claims. (Cl. 260683.74)

This invention relates to an improved process for effecting catalytic conversion of hydrocarbons in liquid phase with fluid catalyst. More particularly, this invention relates to the isomerization of saturated hydrocarbons in liquid phase with a catalyst of the molten salt type, especially such as molten salt mixtures comprising metal salts of the Friedel-Crafts type.

'Ihe liquid phase isomer-ization of normal parans such as butane is well known and has been in commercial use for many years. The process is described for example in the Oil and Gas Journal No. 14, page 151, April 3, 1961. In the past, commercial isomerzation has generally been limited to buia-.ne and, to a lesser extent, pentane since the need heretofore, especially during times of war, has been mainly for the production of aviation gasoline. More recently, however, the demand for high octane motor gasoline has created a need for high-octane, low-boiling components such as isopentane Vand isohexane. Thus, recent emphasis has been on the development of a practical process for isomerizing normal pentane and higher molecular weight normal paratlins for motor gasoline blendma v When isomerizng these higher molecular lweight paraiiins, which are generally only available in hydrocarbon fractions which also contain naphthenes such as' methylcyclopentane, a heavy hydrocarbon fraction containing C8 and C12 hydrocarbon is produced which cannot be completely separated from the catalyst phase by fractionation in a distillation column (generally 'referred toas a catalyst recovery column). Asa consequence, the heavy hydrocarbons are dissolved and entrained in the catalyst phase which is Withdrawn from the bottom of the catalyst recovery column and recycled to the isomerization reactor. The heavy hydrocarbon deaotivates aluminum halide catalyst by forming a complex with the aluminum halide.

Moreover, the addition of fresh aluminum halide is generally etected by dissolving the aluminum halide in part of the recycle catalyst, which is primarily anlimony u'ihalde. When fresh catalyst is added in this manner, substantial quantities of aluminum halide are deactivated, before the catalyst reaches the isomerization reactor, as a result of complexing aluminum halide with heavy hydrocarbon dissolved in the recycle catalyst.

It has now been found in accordance with the present invention that heavy hydrocarbon can be removed from recycle catalyst by extracting the recycle catalyst with light hydrocarbons such as reactor eflluent. In a preferred embodiment of the invention, anextraction zoneis provided at the bottom of the catalyst recovery column wherein the recycle catalyst is extracted with a portion of reactor effluent containing isomerizate. In this manner, recycle catalyst is cooled while reactor eiuent to the catalyst recovery column is heated and the heavy hydrocarbon .is extracted from the recycle catalyst. These and further advantages of the invention will be apparent to those skilled in the art from the following detailed description made with reference to the drawing which is a flow diagram illustrating a preferred embodiment of the process of the invention.

The invention is applicable to the isomerization of C and heaviernormal parailns, preferably a C5 to C7 saturate fraction containing normal paratiins and naphthenes. In order to set forth more fully the nature of the invention, without however intending to limit the scope thereof,

ililg Patented Dec. l5, 1964 ice it will be described in detail as applied to liquid phase isomerization of a CS/CB straight-run fraction with an aluminum chloride-antimony trichloride molten salt catalyst.

Referring now to the drawing, the straight-run feed containing normal paralins and naphthene's is introduced through line 12 and dried in dryer 14. With feeds which are substantially free from Water, dryer 14 will of be unnecessary and can be by-passcd. Auxiliary equipment such as pumps, compressors, heat exchangers, control mechanisms, valves, etc., which are obvious to those skilled in the art are not shown,` Dry feed passes through line 16 into the bottom of catalyst scrubber 18 and rises through the scrubber countercurrently to catalyst pumped from reactor 20 through line 22. The catalyst contains sludge, an aluminum chloride-hydrocarbon complex formed as a result of undesirable side reactions in the reactor. In scrubber 18, antimony trichloride and active aluminum chloride in the catalyst are dissolved in the feed. The sludge, which is insoluble in hydrocarbon, and other contaminants such as corrosion products are removed from the scrubbing zonetbrough line 24. The feed, now containing dissolved catalyst components, is passed through reactor 20 via line 26 together with hydrogen from line 28 and hydrogen chloride from line 30. The reactor can be suitably of the stirred type which has been used in commercial practice but is preferably a vertical tower containing a pool of catalyst 'such as described in Thomas, U.S. Patent 2,983,775, issued May 9, 1961. The catalyst is a molten salt mixture of antimony trichloride and aluminum chloride in appropriate proportions of from about 84 Ito about 98% by weightantimony trichloride and from about 16 to about 2% by weight aluminum chloride. `Temperature in the reaction zone can range from a minimum temperature at which the catalyst can be maintained in the molten state up to approximately 210 F. The isomerization canbe carried out at higher temperatures but the low ltemperatures result in a more desirable yield structure. The pressure in the reaction zone conventionally varies from the pressure required to maintain the C5/C6 fraction primarily in the liquid phase up to any desired super-atmospheric pressure. Pressures from about toA about 500 pounds per square inch gauge generally are suitable.

'Ihe reactor etlluent containing dissolved and entrained catalyst and C5/Cs product hydrocarbon, generally referred to as isomerizate, enters catalyst recovery column 32 through line 34. The catalyst recovery column is suitably a conventional fractional distillation column. Vapor pressure of the antimony trichloride and aluminum chloride is quite low; therefore, separation from the isomenizate is easily effected. The isomerizate is passed overhead as a vapor through line 36, cooled to condense hydrocarbons therein, and collected in accumulator 38.

Hydrogen is Withdrawn from accumulator 38, compressed and recycled through line 28 to reactor 20 as mentioned above. Makeup hydrogen can be added to the system as necessary. Alternatively, it is possible to operate without compression facilities by using once-through hydrogen from a suitable source, such as catalytic reformer or dehydrogenation unit.

Liquid from accumulator 38 is passed via line 40 t0 hydrogen chloride stripping column 42. Hydrogen chloride is recovered overhead and recycled through line 30 to reactop20. Hydrogen chloride can be added to this system as necessary. Liquid isomerizate is removed as a bottom product through line 44. It is desirable to give the isomerizate a caustic treatment and water wash in vessel 46 to remove residual hydrogen chloride or traces of catalyst.

Dissolved and entrained catalyst in the reactor eluent is recovered as catalyst recovery column bottoms and is K dcarbon is' liquid phase introduced into extraction zone 59 vvherein the catalyst is contacted with light hydrocarbon. Boiling point of the light hydrocarbon should be about the same as or slightly below that of the feed hydrocarbons. This is to lfacilitate removal ofthe light hydrocarbon overhead from the catalyst recovery column. The hydrocarbon can suitablyjbe, for example, isomerizate from HC1 stripping column 42 or, isomeriiate from accumulator 38 or, in a preferred embodiment of the invention, the hydrocarbon can be reactor eiiiuent containing isomerizate which is introduced into the extraction zone 50 via line 52. It is preferred to use reactor eluent inorder to realize benefits from heat exchange with the hotcatalyst system. In this manner, itis possible to cool recycle catalyst to Ymore nearly the temperature of the isomerization reactor. The recovered catalyst also extracts a substantial portion of catalyst components from the reactor etiluent. While it is possible to use all of the reactor eiiluent to extract the heavy-hydrocarbon from the catalyst, it is preferred to introduce only a poi-.tion of the eiuent, for example from about 2 to.. about v20% by volume of total eliiuent basis hydrocarbominto the extraction zone.

vThe extraction zone `can be an external, separate vessel or, in a preferred embodiment of the invention, the zone can be an integral part of the bottom of catalyst recovery column32, as shown inthe drawing. While it is not in the practice of the invention, it is preferred to en iplo'y 'nntercurrent extraction techniques in order to', the-maximum benelits of the invention. The extifactio b carried out with or without contact meansy su'ii iacki'ngtraysand the like. v

.Isomerite heavy hydrocarbon'removed.l from theQrec'ycle catalyst passes into'column 32 `wherein separation of isomeri'zate the heavy^ h':ydfswfbfl` is effected. The heavyhydrocarbon forms` a separate' liquid phase. above the vliquid catalyst phase in' the reboil secti'n of the' catalyst fecoverygcolumn. v

l 'withdrawn for example either as av separate from'the catalyst recovery column Vor asa separate liquid phase from reboiler 56 via line 58. They heavy hydrocarbon is preferably treated to remove dissolved catalyst components. Recovered catalyst ,substantially free from heavy hydrocarbon is recycled to isomerization reactor 270 through line 60. The trecycle catalyst or a portion .thereof can suitably be employed to add fresh aluminum halide to theV isomerization system in the manner described previously.

`The following examples are illustrative of *some of the advantagesderivedfrom the invention. K These are not to be considered to limit the scope of the invention.

EXAMPLE I to demonstrate that heavy hydrocarbon, probablyfformed as a result of coupling of 'naphthenes such as methylcyclopentane, isresponsiblefor deactivation of aluminum halide catalysts, three samples were prepared asfollows: 1 (l) Fresh antimony'trichlorideplus 2.5% by Weight aluminum chloride as control sample.

(2) Fresh antimony ichloride, suiiicient C6 piaraiiinic isomerization feed to saturate the antimony trichloride,

`and 2.5 by weight aluminum chloride. v l

(3) Fresh antimony trichloride, suicient heavy hydrocarbony from a catalyst recovery column (obtained during theisornerization of a hexane feed containing naphthenes With analu'minurn chloride-antimony trichloride catalyst) to saturate the antimony trichloride, and 2.5 by Weight aluminum chloride. i v

These samples were maintained at 176 F. for 30 hours. The results of these tests are given in Table I below.

Table I Sample l Sample 2 SampleB (control) (feed) (heavy hy- 'drocarbon) Percent weight complex aluminum chloride v-- 0. 00 0. 03 0. 40

It is evident that heavy hydrocarbon and not isomeriza- .tion feed is responsible for most of the complexing and deactivation of aluminum chloride catalyst.

EXAMPLE II The deleterious effect ofV heavy hydrocarbon such as C8 and C12 hydrocarbon recycle catalyst is demonstrated by the following` test. A C5 saturate feed containing normal paraiiins and naphthenneswas isomerized at 170 F. and 300 p.s.i.g. usingnan aluminum chloride-'antimony trichloride catalystcomposed of 13A-,7% Weight aluminum chloride and (9B-97% vWeightantimony trichlcarid'e.V No catalyst Was recycled fromthe catalyst'recovery column to the .reactorduring this period. y Catalyst losses were balanced by theI addition Qf'alumirium chloride dissolved from l the.iczitalystL recovery' 1100 hours ofV conversion@ dib'rancheuhexane,

ofk eguilibrium) sis of thev malls-cupk s i 1.0% by plexedgaluininm chloride With this manner of' operation'.V chloride- Was complexed in the. make@ systeflt 'a'teof 1.5 4grams per 1 000 feed and complexed in the reactor at a; rate of only about 0.4 graniper 1000 vgrams feed. 'I'Vh's.' when recycle isfused to V'add niak'eupaliriiinuni chloride tothe reactor, a large proportion of the heavy hydrocarbon is complexed with aluminum chloride before entering the reactor. A, i

EXAMPLE tu Some of the advantages ofthe fprcsent irivention.arel illustrated in the following test which Iwas conducted at'Y operating conditions comparable to those used'in Example 1I. During'the first A20,1'1ours, makeup aluminum chloride was dissolved in fresh antimony trichloride and no catalyst was recycled from the 'catalyst recovery column tothe reactor. Thereafter, makeup aluminum chloride was -dissolved in recycle catalyst-which had been eX- tip-acted with isomerizate.- 4After 62 hours of Von-"streain operation, the conversion to dibranched hexane isomers l was about 30% (about 55% of equilibrium) which is approximately thesarne as thefconversion obtained when'A adding fresh aluminum chloride dissolved in fresh anti-4 mony trichloride. As there is no loss in .catalyst activity, reliected by the conversion level, it is evident-that extract-- ing recycle catalysLvith isomerizate removes substantially all ofthe heavy hydrocarbons dissolved in the recycle cata lyst and thereby prevents complexing of fresh aluminum chloride with the heavy hydrocarbons. v

I claim as my invention: Y

l. In an isomerization process wherein a C5 to C7 satu- 'rate fraction containing normal paraliins and naphthenes 1s contacted in a reaction zone with molten salt catalyst comprising aluminumhalide and antimony trihalide and.

reaction zone efluent is separated in a fractionation zone into a vaporous phase containing isomerization Product and a liquid catalyst phase containing heavy hydrocarbon, the improvement which comprises contacting the liquid catalyst phase in an extraction zone with at least a portion of the reactor eiuent, withdrawing from the extraction zone catalyst substantially reduced in concentration of heavy hydrocarbon and using the catalyst for the isomerization of further quantities of normal parat-iin.

2. In an isomerization process wherein a C5 to C7 saturate fraction containing normal paraiiins and naphthenes is contacted in a reaction zone with a molten salt catalyst comprising aluminum chloride and antimony trichloride and reaction zone etiluent is separated in a fractionation zone into a vaporous phase containing isomerization product and a liquid catalyst phase containing heavy hydrocarbon, the improvement which comprises contacting the liquid catalyst phase in an extraction zone with at least a. portion of the reactor eluent, withdrawing from the extraction zone catalyst substantially reduced in concentration of heavy hydrocarbon, dissolving fresh aluminum chloride in at least a portion of the catalyst and using the Catalyst containing aluminum chloride for the isomerization of further quantities of normal parains.

3. In an isomerization process which comprises contacting a C5 to C7 hydrocarbon feed containing normal paratins and naphthenes with a molten salt catalyst comprising aluminum chloride and antimony chloride in a reaction zone, removing a portion of sludge-containing catalyst from the reaction zone and contacting said catalyst with feed hydrocarbons, thereby dissolving soluble catalyst components from the catalyst sludge,

removing reaction zone eluent comprising isomerized hydrocarbons, dissolved catalyst consisting primarily of antimony trichloride, and dissolved heavy hydrocarbon,

separating reaction zone etiluent in a fractionation zone into a vaporous phase containing isomerization product and a liquid phase comprising antimony trichloride and dissolved heavy hydrocarbon,

removing a stream of said liquid phase from the fractionationr zone, dissolving fresh make-up aluminum chloride therein, and returning said stream to the reaction zone,

the improvement which comprises contacting the liquid phase from the fractionation zone prior to addition of fresh aluminum chloride with at least a portion of 4the reaction zone eiuent in an extraction zone, removing from the extraction zone a liquid catalyst phase comprising antimony chloride substantially reduced in heavy hydrocarbon content and a reaction zone etiuent phase enriched in heavy hydrocarbon, and passing the reaction zone eiiiuent phase to the fractionation zone.

References Cited in the tile of this patent UNITED STATES PATENTS 2,394,810 Ross Feb. l2, 1946 2,420,086 McAllister et a1 May 6, 1947 2,927,139 Findlay Mar. l, 1960 2,983,775 Thomas May 9, 1961 

1. IN AN ISOMERIZATION PROCESS WHEREIN A C5 TO C7 SATURATE FRACTION CONTAINING NORMAL PARAFFINS AND NAPHTHENES IS CONTACTED IN A REACTION ZONE WITH MOLTEN SALT CATALYST COMPRISING ALUMINUM HALIDE AND ANTIMONY TRIHALIDE AND REACTION ZONE EFFLUENT IS SEPARATED IN A FRACTIONATION ZONE INTO A VAPOROUS PHASE CONTAINING ISOMERIZATIN PRODUCT AND A LIQUID CATALYST PHASE CONTAINING HEAVY HYDROCARBON, THE IMPROVEMENT WHICH COMPRISES CONTACTING THE LIQUID CATALYST PHASE IN AN EXTRACTION ZONE WITH AT LEAST A PORTION OF THE REACTOR EFFLUENT, WITHDRAWING FROM THE EXTRACTION ZONE CATALYST SUBSTANTIALLY REDUCED IN CONCENTRATION OF HEAVY HYDROCARBON ANBD USING THE CATALYST FOR THE ISOMERIZATION OF FURTHER QUANTITIES OF NORMAL PARAFFIN. 